Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• the present invention relates to a process for the preparation of novel detergent-dispersant additives having a low sulfur content and high TBN which are favorably employed in lubricating oil compositions for internal combustion engines.
• Detergent additives have been used for decades as components of lubricating oil compositions.
• hydroxyaromatic carboxylate salts especially salicylates
• low SAPs Sulfur/Ash/Phosphorus
• U.S. Pat. No. 6,569,818 discloses low sulfur, phosphorus and sulfated ash content lubricating oil compositions containing non-sulfurized alkali metal or alkaline earth metal salts of an alkylsalicylic acid.
• U.S. Pat. No. 2,311,931 discloses metal salts of alkyl or cycloalkyl salicylates sulfides having both excellent detergent and excellent anti-corrosive action when dispersed in lubricating oils and thereby having a single additive effective to inhibit corrosion, sludge and varnish formation, ring sticking and other difficulties experienced in lubricating oils serving in a heavy duty capacity.
• U.S. Pat. No. 2,256,443 discloses a sulfide of an alkyl-substituted hydroxyaromatic carboxylic acid salt having increased pour depressant and viscosity index improving properties.
• the improved antioxidant properties are particularly significant in retarding the development of acidity in certain types of oils and under certain conditions of use.
• U.S. Pat. No. 2,366,873 discloses a sulfide of an alkyl-substituted aryl metal oxide. These sulfides of alkylated aryl metal oxides are characterized by the presence of at least two aromatic nuclei, in which the oxygen of the metal oxide group is attached to the aryl nucleus, which are interconnected by at least one atom of an element selected from the group consisting of sulfur, selenium and tellurium. The compounds exhibit increased effectiveness in retarding the deleterious effects of oxidation in lubricating oil.
• U.S. Pat. No. 2,366,874 discloses a metal salt of an alkylated hydroxyaromatic (phenol) sulfide.
• This compound is a condensation product of an alkyl-substituted aryl metal oxide in which the oxygen of the metal oxide group is directly attached to the aryl nucleus and in which at least two alkyl-substituted aryl nuclei are interconnected by at least one atom of sulfur.
• U.S. Pat. No. 3,410,798 discloses basic metal salts of phenol or salicylic acid sulfides prepared by reacting a phenol or salicylic acid, or a salt thereof, with sulfur and an alkaline earth base at a temperature of about 150° to 200° C., in the presence of a carboxylic acid salt thereof and a polyalkylene glycol or alkylene or polyalkylene glycol alkyl ether.
• the products are useful as detergent additives for lubricants.
• U.S. Pat. No. 3,595,791 discloses basic metal salts of salicylic acid sulfides prepared by reacting salicylic acid, or a salt thereof, with sulfur and an alkaline earth base at a temperature of about 150° to 250° C., in the presence of an alkylene or polyalkylene glycol or a monoether thereof.
• the products are useful as detergent additives for lubricants.
• U.S. Pat. No. 6,235,688 discloses sulfurized phenates, sulfurized salicylates, salts of sulfurized multi-hydroxyl aromatic compounds and chemical and physical mixtures thereof.
• European Patent Publication Number 0168111 discloses sulfurized metal aliphatic hydrocarbon-substituted salicylates, characterized in that an aliphatic hydrocarbon-substituted phenol is sulfurized and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
• European Patent Publication Number 0168110 discloses sulfurized overbased, metal aliphatic hydrocarbon-substituted salicylates by sulfurization of an aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof with a sulfur halide, and subsequently by transforming the reaction product into an overbased metal salicylate.
• European Patent Publication Number 0168880 discloses sulfurized overbased, metal aliphatic hydrocarbon-substituted salicylates, characterized in that an aliphatic hydrocarbon-substituted salicylic acid is transformed into overbased metal salicylate having a basicity index of at least 1.5 by means of a basic metal compound and with carbon dioxide, and subsequently the overbased metal salicylate is sulfurized by heating with elemental sulfur.
• the present invention relates to a process for the preparation of a novel detergent-dispersant additive having a low sulfur content which is favorably employed in lubricating oil compositions for internal combustion engines. More particularly, the present invention relates to a process for the preparation of alkylhydroxybenzoate reaction products, characterized in that the sulfur content ranges from about 0.1 to 1.2 wt % in the alkylhydroxybenzoate reaction product.
• the present invention relates to a process for preparing an alkali metal alkylhydroxybenzoate reaction product comprising the steps of:
• the present invention relates to a process for preparing an alkaline earth metal alkylhydroxybenzoate reaction product comprising the steps of:
• the present invention relates to a process for preparing an overbased alkaline earth metal alkylhydroxybenzoate reaction product obtained by a process comprising the steps of:
• the present invention relates to lubricating oil compositions employing the alkali metal alkylhydroxybenzoate reaction product, the alkaline earth metal alkylhydroxybenzoate reaction product or the overbased alkaline earth metal alkylhydroxybenzoate reaction product, prepared by the respective processes of the present invention described above, with a major amount of base oil of lubricating viscosity.
• the present invention relates to the product prepared by any one of the above processes.
• the present invention provides for a process of producing low sulfur, high TBN detergent-dispersant additives, namely alkylhydroxybenzoate reaction products, that exhibit little to no corrosion in the lubrication of mechanical components of internal combustion engines when employed as detergent-dispersant additives in lubricating oil compositions.
• the lubricating oil compositions employing the detergent-dispersant additives of the present invention are, thus, useful in improving anti-corrosion properties in internal combustion engines operating with such lubricating oil compositions.
• alkali metal or “alkaline metal” refers to lithium, sodium or potassium, with potassium being preferred.
• alkaline earth metal refers to calcium, barium, magnesium and strontium, with calcium being preferred.
• alkyl refers to both straight- and branched-chain alkyl groups.
• alkylphenate means a metal salt of an alkylphenol.
• alkylphenol means a phenol having one or more alkyl substituents, wherein at least one of the alkyl substituents has a sufficient number of carbon atoms to impart oil solubility to the phenol.
• aryl group is a substituted or non-substituted aromatic group, such as the phenyl, tolyl, xylyl, ethylphenyl and cumenyl groups.
• calcium base refers to a calcium hydroxide, calcium oxide, calcium alkoxides, and the like, and mixtures thereof.
• hydrocarbyl means an alkyl or alkenyl group.
• hydrocarbyl phenol refers to a phenol having one or more hydrocarbyl substituents; at least one of which has sufficient number of carbon atoms to impart oil solubility to the phenol.
• lime refers to calcium hydroxide, also known as slaked lime or hydrated lime.
• metal means alkali metals, alkaline earth metals, or mixtures thereof.
• metal base refers to a metal hydroxide, metal oxide, metal alkoxides and the like and mixtures thereof, wherein the metal is selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, strontium, barium or mixtures thereof.
• overbased refers a class of metal salts or complexes. These materials have also been referred to as “basic”, “superbased”, “hyperbased”, “complexes”, “metal complexes”, “high-metal containing salts”, and the like. Overbased products are metal salts or complexes characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal, e.g., a carboxylic acid.
• phenate means a metal salt of a phenol.
• salicylate means a metal salt of a salicylic acid.
• Total Base Number refers to the equivalent number of milligrams of KOH needed to neutralize 1 gram of a product. Therefore, a high TBN reflects strongly overbased products and, as a result, a higher base reserve for neutralizing acids.
• the TBN of a product can be determined by ASTM Standard No. D 2896 or equivalent procedure.
• the present invention relates to a process for preparing an alkylhydroxybenzoate reaction product having low sulfur content favorably employed in lubricating oil compositions for internal combustion engines.
• the alkylhydroxybenzoate reaction product will have a sulfur content from about 0.1 to 1.2 wt % sulfur, more preferably about 0.1 to 1.0 wt % sulfur, and most preferably about 0.1 to 0.5 wt % sulfur in the alkylhydroxybenzoate reaction product of the present invention.
• an alkali metal alkylhydroxybenzoate reaction product of the present invention may be prepared by the following process.
• At least one alkylphenol is neutralized using an alkali metal base in the presence of suitable solvent such as aliphatic hydrocarbons, e.g. toluene, xylene, light alkylbenzene or the light.
• suitable solvent such as aliphatic hydrocarbons, e.g. toluene, xylene, light alkylbenzene or the light.
• the solvent forms an azeotrope with water.
• the solvent may also be a mono-alcohol such as 2-ethylhexanol. In this case, the 2-ethylhexanol is eliminated by distillation before carboxylation.
• the alkylphenol may contain up to 98 wt % linear alkyl groups, up to 100 wt % branched alkyl groups, or both linear and branched alkyl groups.
• the linear alkyl group if present, is alkyl, and the linear alkyl group contains from about 12 to 40 carbon atoms, preferably from about 20 to 40 carbon atoms and more preferably from about 22 to 30 carbon atoms.
• the branched alkyl group, if present, is preferably alkyl and contains at least 9 carbon atoms, preferably from about 9 to 24 carbon atoms and more preferably from about 10 to 18 carbon atoms.
• the alkylphenol contain up to 85 wt % of linear alkylphenol (preferably at least 35 wt % linear hydrocarbyl phenol) in mixture with at least 15 wt % of branched alkylphenol.
• alkylphenol containing up to at least 35 wt % of long linear alkylphenol is particularly attractive because a long linear alkyl chain promotes the compatibility and solubility of the additives in lubricating oils.
• long linear alkyl chain promotes the compatibility and solubility of the additives in lubricating oils.
• relatively heavy linear alkyl groups in the alkylphenols makes the latter less reactive than branched alkylphenols, hence the need to use harsher reaction conditions to bring about their neutralization by an alkaline-earth metal base.
• Branched alkylphenols can be obtained by reaction of phenol with a branched olefin, generally originating from propylene. They consist of a mixture of monosubstituted isomers, the great majority of the substituents being in the para position, very few being in the ortho position, and hardly any in the meta position. That makes them relatively reactive towards an alkaline-earth metal base, since the phenol function is practically devoid of steric hindrance.
• linear alkylphenols can be obtained by reaction of phenol with a linear olefin, generally originating from ethylene. They consist of a mixture of monosubstituted isomers in which the proportion of linear alkyl substituents in the ortho, meta, and para positions is much more uniformly distributed. This makes them much less reactive towards an alkaline-earth metal base since the phenol function is much less accessible due to considerable steric hindrance, due to the presence of closer and generally heavier alkyl substituents.
• linear alkylphenols may contain alkyl substituents with some branching which increases the amount of para substituents and, resultantly, increases the relative reactivity towards alkaline earth metal bases.
• the alkylhydroxybenzoate reaction product of the present invention may contain a mixture of linear alkyl groups, a mixture of branched alkyl groups, or a mixture of linear and branched alkyl groups.
• the alkylphenol can be a mixture of linear aliphatic groups, preferably alkyl; for example, an alkyl group selected from the group consisting of linear C 14 -C 16 , C 16 -C 18 , C 18 -C 20 , C 20 -C 22 , C 20 -C 24 and C 20 -C 28 alkyl and mixtures thereof.
• these mixtures include at least 95 mole %, preferably 98 mole % of alkyl groups and originating from the polymerization of ethylene.
• the alkylhydroxybenzoate reaction product of the present invention having a mixture of alkyl groups, can be prepared from linear alpha olefin cuts, such as those marketed by Chevron Phillips Chemical Company under the names Normal Alpha Olefin C 26 -C 28 or Normal Alpha Olefin C 20 -C 24 , by British Petroleum under the name C 20 -C 26 Olefin, by Shell Chimie under the name SHOP C20-C22, or mixtures of these cuts or olefins from these companies having from about 20 to 28 carbon atoms.
• linear alpha olefin cuts such as those marketed by Chevron Phillips Chemical Company under the names Normal Alpha Olefin C 26 -C 28 or Normal Alpha Olefin C 20 -C 24 , by British Petroleum under the name C 20 -C 26 Olefin, by Shell Chimie under the name SHOP C20-C22, or mixtures of these cuts or olefins from these companies having from about 20 to 28 carbon atoms.
• the alkali metal bases that can be used for carrying out this step include the oxides or hydroxides of lithium, sodium or potassium.
• potassium hydroxide is preferred.
• An objective of this step is to have an alkylphenate having less than 2000 ppm, preferably less than 1000 ppm and more preferably less than 500 ppm of water.
• This operation is carried out at a temperature high enough to eliminate water.
• the product is put under a slight vacuum in order to utilize a lower reaction temperature.
• the neutralization operation is carried out at a temperature of at least 120° C. preferably at least 130° C. and more preferably at least 135° C. for about 3 hours.
• the reaction is conducted at a temperature between 130° C. and 155° C., under an absolute pressure of 800 mbar (8 ⁇ 10 4 Pa).
• the reaction is conducted at a temperature of at least 160° C., as the boiling point of 2-ethylhexanol (184° C.) is significantly higher than xylene (140° C.).
• the pressure is reduced gradually below atmospheric in order to complete the distillation of water reaction.
• the pressure is reduced to no more than 7000 Pa (70 mbar).
• the neutralization reaction is carried out without the need to add a solvent and forms an azeotrope with the water formed during this reaction.
• temperature is heated up to 200° C. and then the pressure is reduced gradually below atmospheric.
• the pressure is reduced to no more than 7000 Pa (70 mbar).
• Elimination of water is done over a period of at least 2 hours, preferably at least 3 hours.
• the alkylphenate prepared is then carboxylated by simply bubbling carbon dioxide into the reaction medium originating from the preceding neutralization step and is continued until at least 50 mole %, preferably 70 mole %, more preferably 80 mole % and most preferably 90 mole %, of the starting alkylphenol has been converted to alkali metal alkylhydroxybenzoate reaction product (measured as salicylic acid by potentiometric determination) at a temperature between about 120° C. and 180° C., under a pressure within the range of from about above atmospheric pressure to 5 ⁇ 10 5 Pa (5 bars) for a period of from about 2 to 8 hours. It must take place under pressure in order to avoid any decarboxylation of the alkali metal alkylhydroxybenzoate that forms.
• the temperature is preferably between about 125° C. and 165° C., more preferably about 130° C. to 155° C. and the pressure is from about atmospheric to 10 bars (10 ⁇ 10 5 Pa), preferably from about atmospheric to 3.5 bars.
• the temperature is directionally lower, preferably from about 110° C. to 155° C. Most preferably from about 120° C. to 140° C. and the pressure from about 1 bar to 20 bars, preferably from about 3.5 bars to 15 bars.
• the carboxylation is usually carried out, diluted in a solvent such as hydrocarbons or alkylate, e.g., benzene, toluene, xylene and the like.
• a solvent such as hydrocarbons or alkylate, e.g., benzene, toluene, xylene and the like.
• the weight ratio of solvent:hydroxybenzoate is from about 0.1:1 to 5:1, preferably from about 0.4:1 to 3:1.
• no solvent is used.
• carboxylation is conducted in presence of diluent oil in order to avoid a too viscous material.
• the weight ratio of diluent oil:hydroxybenzoate is from about 0.1:1 to 2:1, preferably from about 0.2:1 to 1:1 and more preferably from about 0.2:1 to 0.5:1.
• At least one of the alkylphenol, alkylphenate and alkylhydroxybenzoate is reacted with a sulfur source that readily provides sufficient sulfur such as elemental sulfur or sulfur halides as, for example, sulfur chloride (S 2 Cl 2 ), sulfur di-chloride (SCl 2 ) or thionyl chloride (SOCl 2 ).
• the sulfur source is elemental sulfur.
• the formation of the low sulfurized alkali metal alkylhydroxybenzoate reaction product is obtained with reaction of at least one of the alkylphenol, alkylphenate and alkylhydroxybenzoate with, for example, elemental sulfur from a temperature of about 150° C. to 230° C. for a period of about 0.5 to 4 hours, preferably from about 180° C. to 210° C. for a period from about 1 to 3 hours.
• the alkali metal alkylhydroxybenzoate reaction product of the present invention has a TBN from about 50 to 250, more preferably from about 70 to 200 and most preferably from about 100 to 150.
• the alkali metal alkylhydroxybenzoate prepared by the steps of A and B above is further reacted with a molar excess of an alkaline earth metal base to form an alkaline earth metal alkylhydroxybenzoate reaction product according to step C described in the following.
• the objective of this step is to acidify the alkali metal alkylhydroxybenzoate salt diluted in the solvent to give an alkylhydroxybenzoic acid. Any acid stronger than alkylhydroxybenzoic acid could be utilized. Usually aqueous hydrochloric acid or aqueous sulfuric acid is utilized.
• the acidification step is conducted with an H + equivalent excess of acid versus hydroxybenzoic (salicylic) of at least 5 H+ equivalent %, preferably 10 H+ equivalent %, and more preferably 20 H+ equivalent %.
• sulfuric acid is used. It is diluted to about 5% to 50%, preferably about 10% to 30%.
• the quantity of sulfuric acid used versus hydroxybenzoate (salicylate), on a per mole of hydroxybenzoate basis, is at least 0.525 mole, preferably 0.55 mole and more preferably 0.6 mole of sulfuric acid.
• the acidification reaction is carried out under agitation with any suitable mixing system at a temperature from about room temperature to 120° C., preferably from about 50° C. to 80° C., at a period from about 15 minutes to 300 minutes, preferably from about 60 minutes to 180 minutes.
• the agitation is stopped in order to allow good phase separation before the aqueous phase is separated.
• At least one of the alkylphenol, alkylphenate, alkylhydroxybenzoic acid and alkylhydroxybenzoate is reacted with a sulfur source as described above for the first embodiment.
• the alkaline metal alkylhydroxybenzoate reaction product of the present invention has a TBN from about 50 to 250, more preferably from about 70 to 200 and most preferably from 100 to 150.
• the alkaline earth metal alkylhydroxylbenzoate prepared by the steps of A through C above is further overbased with at least one acidic overbasing material to form an overbased alkaline earth metal alkylhydroxybenzoate reaction product according to step D described in the following.
• Overbasing of the alkaline earth metal alkylhydroxybenzoate reaction product may be carried out by any method known by a person skilled in the art to produce an overbased alkaline earth metal alkylhydroxybenzoate reaction product.
• the overbasing reaction is carried out in a reactor in the presence of diluent oil, an aromatic solvent and an alcohol.
• the reaction mixture is agitated and alkaline earth metal and at least one acidic overbasing material such as carbon dioxide are added to the reaction while maintaining the temperature between about 20° C. and 80° C.
• the degree of overbasing may be controlled by the quantity of the alkaline earth metal, at least one acidic overbasing material such as carbon dioxide and the reactants added to the reaction mixture and the reaction conditions used during the carbonation process.
• the ratios of reagents used (methanol, xylene, slaked lime and CO 2 ) will correspond to the following weight ratios:
• the alkaline earth metal alkylhydroxybenzoate reaction product is then overbased with an alkaline earth metal base to form the overbased alkaline earth metal alkylhydroxybenzoate reaction product of the present invention.
• Alkaline earth metals such as barium, calcium, magnesium and strontium are preferred. Calcium hydroxide or oxide is preferred.
• lime is added as a slurry, i.e., as a pre-mixture of lime, methanol, xylene, and CO 2 is introduced over a period of 1 hour to 4 hours, at a temperature between about 20° C. and 65° C.
• At least one of the alkylphenol, alkylphenate, alkylhydroxybenzoic acid and alkylhydroxybenzoate or overbased derivatives thereof is reacted with a sulfur source as described above for the first embodiment.
• predistillation, centrifugation and distillation may be utilized to remove solvent and crude sediment.
• Water, methanol and a portion of the xylene may be eliminated by heating between 110° C. to 134° C. This may be followed by centrifugation to eliminated unreacted lime.
• xylene may be eliminated by heating under vacuum in order to reach a flash point of at least about 160° C. as determined with the Pensky-Martens Closed Cup (PMCC) Tester described in ASTM D93.
• PMCC Pensky-Martens Closed Cup
• the overbased alkaline earth metal alkylhydroxybenzoate of the present invention has a TBN from about 20 to 500, more preferably from about 100 to 400 and most preferably from about 150 to 300.
• the present invention also relates to lubricating oil compositions containing the alkylhydroxybenzoate reaction products of the present invention.
• the lubricating oil composition of the present invention may comprise a major amount of a base oil of lubricating viscosity and a minor amount of an alkali metal alkylhydroxybenzoate reaction product obtained by a process comprising the steps of:
• the lubricating oil composition of the present invention may also comprise a major amount of a base oil of lubricating viscosity and a minor amount of an alkaline earth metal alkylhydroxybenzoate reaction product obtained by a process comprising the steps of:
• the lubricating oil composition of the present invention may further comprise a major amount of a base oil of lubricating viscosity and a minor amount of an overbased alkaline earth metal alkylhydroxybenzoate reaction product obtained by a process comprising the steps of:
• Base oil as used herein is defined as a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
• Base stocks may be manufactured using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use.
• the base oil of this invention may be any natural or synthetic lubricating base oil fraction particularly those having a kinematic viscosity at 100° Centigrade (° C.) and about 4 centistokes (cSt) to about 20 cSt.
• Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene, polyalphaolefin or PAO, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fisher-Tropsch process.
• a preferred base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity about 20 cSt or higher at about 100 C.
• Oils used as the base oil will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g. a lubricating oil composition having an SAE Viscosity Grade of 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.
• SAE Viscosity Grade 0W, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.
• the base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.
• Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
• Suitable base oils include those in all API categories I, II, III, IV and V as defined in API Publication 1509, 14th Edition, Addendum I, December 1998. Saturates levels and viscosity indices for Group I, II and III base oils are listed in Table I.
• Group IV base oils are polyalphaolefins (PAO).
• Group V base oils include all other base oils not included in Group I, II, III, or IV.
• Group III base oils are preferred.
• Natural lubricating oils may include animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
• vegetable oils e.g., rapeseed oils, castor oils and lard oil
• petroleum oils e.g., mineral oils, and oils derived from coal or shale.
• Synthetic oils may include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and inter-polymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogues and homologues thereof, and the like.
• Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc.
• Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols.
• Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
• Tri-alkyl phosphate ester oils such as those exemplified by tri-n-butyl phosphate and tri-iso-butyl phosphate are also suitable for use as base oils.
• Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
• Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
• the base oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
• Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sand bitumen) without further purification or treatment.
• Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which may then be used without further treatment.
• Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
• Suitable purification techniques include distillation, hydrocracking, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
• Rerefined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
• Base oil derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base oil.
• Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
• a major amount of base oil as defined herein comprises 40 wt % or more.
• Preferred amounts of base oil comprise about 40 wt % to about 97 wt %, preferably greater than about 50 wt % to about 97 wt %, more preferably about 60 wt % to about 97 wt % and most preferably about 80 wt % to about 95 wt % of the lubricating oil composition. (When weight percent is used herein, it is referring to weight percent of the lubricating oil unless otherwise specified.)
• the amount of alkylhydroxybenzoate reaction product of the present invention in the lubricating oil composition will be in a minor amount compared to the base oil of lubricating viscosity. Generally, it will be in an amount from about 1 to 15 wt %, preferably from about 2 tol 2 wt % and more preferably from about 3 to 8 wt %, based on the total weight of the lubricating oil composition.
• the lubricating oil compositions according to the present invention will have a TBN from about 5 to 80, preferably from about 10 to 70 and more preferably from about 15 to 50.
• additive components are examples of components that can be favorably employed in combination with the lubricating additive of the present invention. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
• Ashless dispersants alkenyl succinimides, alkenyl succinimides modified with other organic compounds, and alkenyl succinimides modified with boric acid, alkenyl succinic ester.
• Phenol type phenolic) oxidation inhibitors 4,4′-methylenebis (2,6-di-tert-butylphenol),4,4′-bis(2,6-di-tert-butylphenol), 4,4′-bis(2-methyl-6-tert-butylphenol), 2,2′-(methylenebis(4-methyl-6-tert-butyl-phenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-nonylphenol), 2,2′-isobutylidene-bis(4,6-dimethylphenol), 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl4-methylphenol, 2,6-di-tert-butyl4-ethylphenol, 2,4-dimethylmethyl
• Diphenylamine type oxidation inhibitor alkylated diphenylamine, phenyl- ⁇ -naphthylamine, and alkylated ⁇ -naphthylamine.
• metal dithiocarbamate e.g., zinc dithiocarbamate
• methylenebis dibutyldithiocarbamate
• Nonionic polyoxyethylene surface active agents polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol mono-oleate, and polyethylene glycol monooleate.
• Demulsifiers addition product of alkylphenol and ethyleneoxide, polyoxyethylene alkyl ether, and polyoxyethylene sorbitane ester.
• E Extreme pressure agents: zinc dialkyldithiophosphate (Zn-DTP, primary alkyl type & secondary alkyl type), sulfurized oils, diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane, and lead naphthenate.
• Zn-DTP zinc dialkyldithiophosphate
• Sn-DTP primary alkyl type & secondary alkyl type
• sulfurized oils diphenyl sulfide, methyl trichlorostearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane, and lead naphthenate.
• Friction modifiers fatty alcohol, fatty acid, amine, borated ester, and other esters
• Multifunctional additives sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound, and sulfur-containing molybdenum complex compound
• Viscosity Index improvers polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and dispersant type viscosity index improvers.
• (K) Foam Inhibitors alkyl methacrylate polymers and dimethyl silicone polymers.
• the reactor was then heated further to 145° C. over a period of about 2 hours, then gradually decreasing the atmospheric pressure (1013 mbar absolute ⁇ 1 ⁇ 10 5 Pa) to 800 mbar absolute (8 ⁇ 10 4 Pa). Under these conditions, reflux was maintained for 3 hours and the vacuum was broken with nitrogen to decrease the pressure down to atmospheric pressure. The reactor was heated to about 200° C. over a period of one hour and held for 90 minutes at these conditions. A potassium alkylphenate containing 30% xylene was obtained and was stored under nitrogen.
• the low sulfurized potassium alkylhydroxybenzoate was reacted with a 30 molar % excess of aqueous solution of sulfuric acid to convert it to a sulfurized alkylhydroxybenzoic acid as follows:
• a mixture of 100.8 g of sulfuric acid at 95% and 907.2 g of water in order to obtain 1008 g of a solution of sulfuric acid diluted at 10% was placed in a 6 liter reactor and heated to 50° C. under agitation at 250 rpm.
• the low sulfurized potassium alkylhydroxybenzoate from step B above and xylene (970 g) were loaded over a period of 30 minutes.
• the reactor was heated and maintained at 60° C. to 65° C. for 2 hours with continued agitation.
• the upper organic phase containing the low sulfurized alkylhydroxybenzoic acid and xylene were collected for the following step.
• the concentration of low sulfurized alkylhydroxybenzoic acid was determined as an equivalent of mg KOH/g.
• the reactor was heated to 40° C. over a period of 30 minutes, and a mixture of formic acid (5.4 g):acetic acid (5.4 g) was added and allowed to react with the contents in the reactor. After a period of 5 minutes, the reactor was cooled to 30° C. over a period of 30 minutes. The reaction yielded a calcium alkylhydroxybenzoate reaction product.
• the mixture contained within the reactor was taken in stages to a temperature between 65° C. to 128° C. over a period of 110 minutes. This procedure removed methanol, water and a portion of the xylene. Once 128° C. was reacted, diluent oil of Group II having less than 0.03% of sulfur (161 g) was added. Crude sediment was then measured. The amount of crude sediment in the low sulfurized overbased calcium alkylhydroxybenzoate reaction product was 1.2 volume %. The reaction mixture was centrifuged to remove crude sediment and then distilled at 204° C. for 10 minutes under vacuum at 50 mbar absolute (50 ⁇ 10 2 Pa) to remove the remaining xylene.
• the corrosion property of the alkylhydroxybenzoate reaction products were evaluated in the Copper Strip Corrosion Test as specified in ASTM D130.
• Crude petroleum contains sulfur compounds, most of which are removed during refining. However, of the sulfur compounds remaining in the petroleum product, some can have a corroding action on various metals and this corrosivity is not necessarily related directly to the total sulfur content. The effect can vary according to the chemical types of sulfur compounds present.
• the copper strip corrosion test is designed to assess the relative degree of corrosivity of a petroleum product. In this test, a polished copper strip is immersed in a specific volume of the sample being tested and heated under conditions of temperature and time that are specific to the class of material being tested. At the end of the heating period, the copper strip is removed, washed and the color and tarnish level assessed against the ASTM Copper Strip Corrosion Standard summarized below.
• Equipment DSC 2920 supplied by TA instruments.
• Oxidative properties were evaluated by a:
• Carboxylation CO 2 (g) 42 42 42 42 C. Acidification S-Carboxylate 1100 1100 1100 1100 Xylene (g) 970 970 970 970 Sulfuric acid at 45% (g) 100.8 100.8 100.8 100.8 Water (g) 907.2 907.2 907.2 D.
• Example 3 The results shown on Table III demonstrate that Examples 1 and 2 of the present invention, having a lower sulfur wt %, show significantly reduced levels of sediment and copper corrosion than comparative Example A. Having low sulfur (Example 2) also provides improved oxidation resistance as compared to no sulfur (Comparative Example B).

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